1. Field of the Invention
The present invention pertains to novel fused ring structures useful for providing a platform for novel explosive and pyrotechnic compounds, particularly high nitrogen content, low carbon content energetic compounds, dyes, pharmaceutical and other compositions. The present invention includes a precursor compound pertaining to a 1,2,4-Triazolo[4,3-a][1,3,5]Triazine compound, particularly a 1,2,4-Triazolo[4,3-a][1,3,5]Triazine-3,5,7-Triamine, and novel fused ring structures such as triazolyl-tetrazinyl-aminotriazine compounds, and complexes and salts thereof, and other such chemical structures as detailed herein.
2. Brief Description of the Related Art
Development of specialized chemical compounds requires proper precursor chemical structures.
Current methods that purport to synthesize 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine all involve heating dicyandiamide and hydrazine dihydrochloride at elevated temperatures (100xc2x0 C. or higher) for significant amounts of time in order to condense the dicyandiamide. This method was described by Kaiser et al. in a paper published in the Journal of Organic Chemistry, Vol. 18, 1953, page 1610.
Using this synthesis method theoretically provides for two possible isomeric structures of triazolotriazinetriamine (see I and II below). The first structure is the [4,3-a]triazolotriazinetriamine, pictured below as I. The second structure is the [1,5-a]triazolotriazinetriamine, pictured below as II. The product by Kaiser et al., resulting from the method above, was assigned the structure of I based upon degradation/oxidation studies of the product. However, these types of studies provide for a large degree of uncertainty as to structure. 
Recently, product derived from the above process was tested using X-ray diffraction, an extremely reliable technique, and, rather than the expected product I as originally reported, it was found that the actual structure of the product was that of II. The commercial product based upon the above method, sold under the names 3,5,7-triamino-s-triazolo[4,3-a]-s-triazine or 3,5,7-triamino-1,2,4-triazolo[4,3-a]-1,3,5-triazine, has also been tested via X-ray diffraction and found to be the structure of II. Because of the above error, prior to the present invention, there is, therefore, no known process of synthesizing product I. Additionally, patents such as U.S. Pat. No. 3,939,084 to Sullivan purport to use a 3,5,7-Triamino-s-trizazolo(4,3-a)-s-triazine, as well as articles such as xe2x80x9cNew Synthesis of Dyes of the Triazinexe2x80x9d, Series II. VAT Dyes of the Triazolo-Triazine Series by A. Titkov and I. D. Pletnev, Scientific Research Institute of Intermediates and Dyes, translated from Zhurnal Obshchel Khimil, Vol. 33, No. 4, pp. 1355-1357, April 1963 (see also Maeda et al. Japan Kokai 74 24,226 and 74 27,287), which are apparent mislabelings of the 3,5,7-Triamino-s-trizazolo(1,5-a)-s-triazine).
The effects of the structural difference between these two products on the chemical and physical properties are of interest in any application of monotriazolotriazine ring systems. Of particular interest for energetic uses of these products would be the energy release in detonation, which correlates to the density of the materials. An analysis of densities and potential energy releases of the products reveals that the product I has a higher potential energy release value than product II that is significant in defense related energetic systems. The product II has also been investigated for use in the dye industry as a chromophore coupled to anthraquinones and indoles, and, therefore, product I should have similar potential uses. Other aromatic structure systems also are of interest.
Due to the discovery that the chemical sold as product I is actually product II, and the chemical and physical properties of the two products are significant for many uses, it would be desirable to derive product I, and like compounds, provide for synthesis such compounds, as well as developing compounds from processes using product I and like compounds as a precursor.
The present invention includes a novel compound structure having the formula: 
wherein R1 is xe2x80x94NH2, and R2 and R3 are independently electron donating groups, preferably where R1, R2 and R3 are xe2x80x94NH2.
The present invention further includes a novel fused ring structure having the formula: 
wherein R4 is a substituent being or replacing the xe2x80x94NH2 of the precursor, preferably being an electron donating group, and more preferably being xe2x80x94NH2, and R5 is a ring having greater than five atoms within the ring, preferably where R4 is xe2x80x94NH2 and R5 forms a six-member or seven-member ring, more preferably with such ring having three or more nitrogen atoms. The ring may include substituents thereon.
The present invention also includes a pyrotechnic composition comprising a compound having the chemical structure: 
wherein Z+ comprises H+ or a cation; R comprises a complexing component; and,
wherein m=1, 2 or 3; n=0, 1, 2 or 3; x=0, 1, 2 or 3; and t=0 or 1. The structure provides the complex and salt forms of triazolyl-tetrazinyl-aminotriazine. The present invention further includes a method of making a pyrotechnic composition comprising a triazolyl-tetrazinyl-aminotriazine compound comprising the steps of providing a triazolyl-triaminotriazine precursor and diazotizing the precursor to form the triazolyl-tetrazinyl-aminotriazine, or derivative thereof. Additionally, the present invention further includes a pyrotechnic composition comprising a triazolyl-tetrazinyl-aminotriazine compound.
The present invention further includes a dye comprising a formula of: 
wherein R2 and R3 independently comprise electron donating groups, and Rx comprises an elongated conjugation sufficient to create a chromogen, with Rx preferably a chromophore, including azo dyes, having a (xe2x80x94Nxe2x95x90Nxe2x80x94) linkage or an imino dyes having a (xe2x80x94Nxe2x95x90CRaRbxe2x80x94) linkage, such as (xe2x80x94Nxe2x95x90CRaArxxe2x80x94), where Ra and Rb represent additional dye forming substituents, such as aryl groups, e.g., multiple and/or fused aryl groups (Arx).
Preferably the dye comprises the formula of: 
wherein R9, R6, R7, and R8 are electron donating groups, more preferably with R6 and R7 being xe2x80x94NH2, and most preferably with R9, R6, R7, and R8 are xe2x80x94NH2; and Ry is xe2x80x94Nxe2x95x90Nxe2x80x94.
The present invention includes a process for making a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, acid salt, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt and a process for neutralizing the acid salt to make a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, as well as the product of this process (the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, including the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine is referred to herein as the xe2x80x9cprecursorxe2x80x9d). Because of the reactive properties of the precursor, this precursor is useful in deriving compounds for ingredients in propellants, explosives, pyrotechnics, gas generators, ultraviolet absorbers, pharmaceuticals, and colorants, as later described.
The general process involves ring closure of a 2,4-substituted diamino-6-hydrazino-s-triazine with an acid and a chemical of the general formula RCN where the R comprises a leaving group, and then neutralizing said acid. Because the hydrazine nitrogen atoms that form the triazole ring are already in place on the 2,4-substituted-6-hydrazino-s-triazine, the final product formed is the desired [4,3-a] isomer, rather than the [1,5-a] isomer produced by the conventional dicyandiamide/hydrazine dihydrochloride methods. The general formulas for the process are set forth below: 
wherein the R comprises a leaving group, and R2 and R3 comprise electron donating groups.
More specifically, first, the invention comprises a process for the preparation of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, acid salt, with an amino group at the 3-position. In order to practice the present invention, one may first obtain or synthesize 2,4-diamino-6-hydrazino-s-triazine. One method for synthesizing this chemical is set forth in U.S. Pat. No. 3,061,605 by D""Alelio. The general method is to effect a reaction between 2,4-diamino-6-chloro-1,3,5-triazine and hydrazine. A specific example is set forth in column 3, lines 60-70 of the above patent and are hereby incorporated by reference. While this particular method of synthesizing 2,4-diamino-6-hydrazino-s-triazine is specifically disclosed, any prior art method of synthesis would be appropriate to practice the present invention.
The first step in the present invention comprises dissolving the 2,4-diamino-6-hydrazino-s-triazine with an acid. This step is preferably carried out at room temperature with an acid that is of sufficient strength to dissolve the 2,4-diamino-6-hydrazino-s-triazine. Many acids can be employed in the present invention, such as sulfuric acid or hydrochloric acid or mixtures of these acids with other solvents such as methanol or ethanol, and may be selected by one skilled in the art. One preferred acid is 1N hydrochloric acid.
The second step comprises mixing the dissolved 2,4-diamino-6-hydrazino-s-triazine with a reagent of the formula RCN, wherein R comprises a leaving group. This reaction will provide the amino triazole ring on the product directly. A leaving group, as used in this application, is a group that can be displaced to give ring closure; that is, produces the amino triazole ring. One preferred leaving group comprises bromine wherein the reagent comprises cyanogen bromide. Although the reaction in this step is acid catalyzed, preferred reaction times range from about twenty hours to about thirty hours in order to allow for the maximum formation of acid salt crystals. It is also preferred that the acid salt crystals be removed after the reaction is substantially complete, approximately thirty hours, to prohibit contamination of the final product with impurities. The crystals may be removed by any normal method, such as filtration, and can then be washed and dried in order to obtain the final acid salt product.
The present invention also comprises a process to take the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt synthesized above, and neutralize the acid salt crystals in order to obtain a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This process involves the steps described above as well as the following steps.
First, the acid salt crystals are removed from the solution synthesized above. Then, the acid salt crystals are neutralized by mixing them with a substance more basic than 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This step results in the removal of the acid from the above reaction and provides for a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The substance used in this final step may be selected by one skilled in the art based upon the basicity of the substance versus the basicity of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. Some examples are potassium carbonate, potassium acetate, sodium bicarbonate, and sodium hydroxide. One preferred substance is potassium carbonate. It is also take place in solution, so preferably, water or some other solvent may be added to the salt.
Due to the reactive nature of the xe2x80x94NH2 from the five-member ring, derivatives of the precursor, particularly tri-cyclic fused compounds as described below, are useful in a wide range of fields, including for example, pharmaceuticals and treating compositions, such as topical lotions including without limitation sunscreen, creams and/or therapeutic liquids, over-the-counter and/or prescription drugs, parental drugs, injectable drugs, food supplements, agricultural compositions, such as without limitation herbicides, pesticides, fungicides and/or fertilizers; ultraviolet (UV) stabilizers and ultraviolet absorbers, colorants such as dyes, pigments and other color applicants, such as without limitation paints, textile colorants and/or indicators, including liquid crystal uses and other indicators for computer display screens, explosives, pyrotechnics and gas generators, such as for use in airbags and other like functions; and/or fluids, such as functional fluids, additives and/or stabilizers, for use in machinery and/or other mechanical applications. The precursor may be used to anchor functional groups, such as benzophenones, benzotriazoles, substituted acrylonitriles and phenol-nickel complexes for ultraviolet absorbers, use of the precursor as an additive for a functional fluid (see e.g., U.S. Pat. No. 3,939,084 to Sullivan purporting to use a 3,5,7-Triamino-s-trizazolo (4,3-a)-s-triazine as an additive (col. 14, Ins. 60-61) in Table I; which is a mislabeled 3,5,7-Triamino-s-trizazolo (1,5-a)-s-triazine), or chromogens as detailed below. For example, triazoles and/or triazines are known in the fields of agriculture (see e.g., U.S. Pat. No. 5,602,075 to Benko et al., herbicides), pharmaceuticals (see e.g., U.S. Pat. No. 5,380,714 to Jones et al., U.S. Pat. No. 5,457,091 to Jaehne et al., U.S. Pat. No. 5,246,932 to Caulkett et al., U.S. Pat. No. 6,107,300 to Bakthavatchalam et al. and U.S. Pat. No. 5,489,591 to Kobayashi et al.), colorants (see e.g., U.S. Pat. Nos. 3,758,309 and 3,725,067 to Bailey et al., U.S. Pat. No. 4,236,003 to Fletcher, and U.S. Pat. No. 4,621,046 to Sato et al.). and agricultural chemicals, medicines, dyes, paints, and the like, as various resin materials, such as aminoplast molded materials and flame retarding materials (see e.g., U.S. Pat. No. 6,127,538 to Tanaka et al.; see col. 1, Ins. 26-30; see also U.S. Pat. No. 5,371,218 to Cipolli et al.).
The present invention further includes a novel fused ring structure having the formula: 
wherein R4 is a substituent being or replacing the xe2x80x94NH2 of the precursor, preferably being an electron donating group, and more preferably being xe2x80x94NH2, and R5 is a ring having greater than five atoms within the ring, preferably where R4 is xe2x80x94NH2 and R5 forms a six-member or seven-member ring, more preferably with such ring having three or more nitrogen atoms. The ring may include substituents thereon.
As used herein, an xe2x80x9celectron donating groupxe2x80x9d designates a group that will release or donate electrons more than hydrogen would if it occupied the same position in the molecule. See J. March, Advanced Organic Chemistry, 3rd Ed., John Wiley and Sons p. 238 (1985). These types of groups are well known in the art. Examples include lower alkylamino, diloweralkylamino, amino, halo, aryl, lower alkoxy. Lower aralkoxy, aryloxy, mercapto, lower alkylthio, and the like, including for example, Oxe2x88x92, xe2x80x94COOxe2x88x92, xe2x80x94OR, xe2x80x94CR3, xe2x80x94OCOR, xe2x80x94NR2, SR, where R group is an alkyl group or H. The preferred electron donating groups are amino, hydroxy, lower alkoxy, lower alkylamino and diloweralkylamino. The most preferred electron donating group is amino. Electron donating groups include atoms that can stabilize the developing positive charge in a ring closure by Mesomeric Effect, such as methoxy groups.
The present invention includes novel triazolyl-tetrazinyl-aminotriazine compounds, and the complexes and salts thereof, that are particularly useful in energetic materials, such as explosive, pyrotechnic and/or gas generator compositions. These triazolyl-tetrazinyl-aminotriazine compounds have special applicability in demolitions, fireworks and airbag inflating compositions. For example, the fireworks compositions of the present invention are characterized as low-smoke compositions and can be formulated to be essentially smoke-free. Low smoke compositions have decreasing amounts of residual smoke after pyrotechnic burn that are operationally and commercially useful. The triazolyl-tetrazinyl-aminotriazine compounds, and their complexes and salts, provide a high-nitrogen
The present invention includes an energetic material, particularly a pyrotechnic composition, comprising a compound having the chemical structure: 
wherein Z+ comprises H+ or a cation; R comprises a complexing component; and, wherein m=1, 2 or 3; n=0, 1, 2 or 3; x=0, 1, 2 or 3; and t=0 or 1.
The complex form of the triazolyl-tetrazinyl-aminotriazine occurs when Z+ comprises H+, with H attached to a nitrogen of the compound, and the value of x is not 0. Complexes of the present invention include, for example, R=Dihydrazino-s-tetrazine, Trihydrazino-s-triazine, 5-Aminotetrazole, N-aminotriazoles, and bis-(1(2)H-tetrazol-5-yl)-amine.
The pyrotechnic compositions of the present invention further include metal and non-metal salts of the triazolyl-tetrazinyl-aminotriazine compound. In one particular embodiment, preferably m=n.
In addition to a complex or salt structure of the triazolyl-tetrazinyl-aminotriazine compound, a useful structure of the triazolyl-tetrazinyl-aminotriazine compound in pyrotechnic compositions includes Z+ being H+, t=1, m=1, n=1, and x=0. When Z+ comprises H+, and m and n are both equal to 1, the calculated heat of compound in pyrotechnic compositions includes Z+ being H+, t=1, m=1, n=1, and x=0. When Z+ comprises H+, and m and n are both equal to 1, the calculated heat of formation is approximately 255 kcal/mole (gas phase), and a density of approximately 1.77 g/cc (calcd) which provides significant energy to the pyrotechnic composition.
The Z+ component of the triazolyl-tetrazinyl-aminotriazine compound preferably comprises a cation. As a salt, the compound may be selected from a large number and/or variety of cations as suitable for any particular pyrotechnic. Suitable cations of the present invention include those appropriate to provide color displays from combusting fireworks, particularly metals or amine salts. Metals of the present invention may include, without limitation sodium (Na), cobalt (Co), copper (Cu), aluminum (Al), nickel (Ni), barium (Ba), strontium (Sr), calcium (Ca), potassium (K), iron (Fe), titanium (Ti), magnesium (Mg), antimony (Sb) and the like. Additionally, typical amine salts may include compounds with Z+ being, without limitation, H2NC(NH2)NHCONH2, C(NHNH2)3, NH2NH3, NH4, H2NNHC(NH2)NH2, (H2NNH)2C(NH2), C(NH2)3, (HONH3), and bis(1(2)H-tetrazol-5-yl)-amine (C2H4N9), the monohydrate of bis(1(2)H-tetrazol-5-yl)-amine (C2H4N9.H2O). Ignition or combustion of Z+ of the present invention preferably results in a color, however, additional salts and other compositions may be added in combination with the triazolyl-tetrazinyl-aminotriazine compounds to form the pyrotechnic compositions, as later described. Use of the metal salts of the triazolyl-tetrazinyl-aminotriazine compounds as colorants within the pyrotechnic compositions may generally include the metals conventionally used in pyrotechnic compositions. For example, strontium, barium, copper, and iron salts of triazolo-tetrazino-aminotriazine compounds, and salts thereof, can be expected to yield red, blue, green, yellow, purple, red-purple, and blue-green colorants.
The following structures exemplify non-limiting examples of possible salts for use in the pyrotechnic compositions of the present invention: 
The pyrotechnic composition generally includes the addition of an oxidant to fully consume the carbon and hydrogen components of the pyrotechnic compositions during burning. Suitable oxidizers can generally include, without limitation, one or more alkaline earth metal nitrates, alkaline earth metal nitrites, alkali metal nitrates, alkali metal nitrites, transition metal oxides, such as ammonium perchlorate, alkali perchlorates such as potassium perchlorate and the like, ammonium nitrate, and alkali nitrates such as potassium nitrate and the like, or combinations thereof Examples of the oxidizer include at least one of an alkali metal or an alkaline earth metal nitrate, a complex salt nitrate, such as Ce(NH4)2 (NO3)6 or ZrO(NO3)2, a dried, hydrated nitrate, such as Ca(NO3)2.4H2O or Cu(NO3)2.2.5 H2O, silver nitrate, an alkali or alkaline earth metal chlorate or perchlorate, ammonium perchlorate, a nitrite of sodium, potassium, or silver. Additionally, organic compositions such as a solid organic nitrate, nitrite, or amine, such as guanidine nitrate, nitroguanidine and 5-aminotetrazole may be included. The oxidizer may include silver nitrate or a co-melt or mixture comprising silver nitrate and at least one of an alkali metal nitrate, an alkaline earth metal nitrate, a complex salt nitrate, a dried, hydrated nitrate, an alkali metal chlorate, an alkali metal perchlorate, an alkaline earth metal chlorate, an alkaline earth metal perchlorate, ammonium perchlorate, sodium nitrite, potassium nitrite, silver nitrite, or a complex salt nitrite; and independently a solid organic nitrate, a solid organic nitrite, or a solid organic amine. Alkali chlorates are generally not preferred as oxidizer due to sensitivity concerns. Ammonium perchlorate and ammonium nitrate are preferred oxidizers as the absence of any metal ions is better for control of the fireworks color and eliminates any ash residue. Ammonium perchlorate is particularly preferred as the oxidizer to provide a source of chlorine ions to the pyrotechnic composition. Chlorine ion may be supplied by addition of a metal chloride salt as the colorant or by use of ammonium perchlorate as the oxidizer, or a part thereof. Ammonium nitrate is hygroscopic and compositions including ammonium nitrate must be protected from moisture.
The oxidizer is generally added with the triazolyl-tetrazinyl-aminotriazine compounds, or their complexes or salts, in amounts sufficient to provide about three equivalents of free oxygen. For example, the ammonium perchlorate oxidizes the triazolyl-tetrazinyl-aminotriazine anion to carbon dioxide and water if in a ratio of two parts by weight ammonium perchlorate to one part of the organic anion. The same degree of oxidation requires four parts ammonium nitrate. Generally, the compositions can include from about 30 percent by weight to about 60 percent by weight of the high-nitrogen content, low-carbon content energetic material, more preferably from about 35 percent by weight to about 55 percent by weight, together with about 40 to about 60 percent by weight of the selected oxidizer.
As previously described, the pyrotechnic may further include a colorant in addition to the triazolyl-tetrazinyl-aminotriazine complex or salt. Colorants may be additional metal salts, or other compositions, as known in the art. For example, each metal salt has an anticipated colorant effect within a pyrotechnic composition, as each metal has well-known spectra associated with the burning of that metal. These include strontium salts such as strontium nitrate (Sr(NO3)2) or strontium carbonate (SrCO3) for the color red, calcium salts such as calcium carbonate for the color red-orange, barium salts such as barium nitrate (Ba(NO3)2), barium chlorate (Ba(ClO3)2) or boron compounds for the color green, sodium salts such as sodium nitrate for the color orange-yellow, or sodium oxalate (Na2C2O4) or cryolite (3NaF.AlF3) for yellow, copper salts such as copper oxide, CUCO3, Paris Green [CuAs2O4.Cu(Ac)2] for the color blue, potassium salts such as potassium chloride for the color purple or violet, and magnesium, aluminum, antimony salts such as antimony sulfide (Sb2S3) for the color white. Combinations of these and other metal salts may be used to provide additional colors, such as orange from a combination of calcium carbonate and sodium nitrate, red-purple from a combination of copper sulfide and strontium nitrate, and yellow from a combination of barium nitrate and sodium nitrate. Other metal salts such as cadmium, uranium, gold, mercury, arsenic, iron and lead may be used to provide other colors if desired, although many such salts are not generally preferred due to toxicity. Nitrate salts are generally more preferred than chloride salts as chloride salts tend to occur as hydrates and thus contribute undesired water. The colorant is generally added in amounts from about 0.5 percent by weight to about 20 percent by weight, preferably from about 1 percent by weight to about 10 percent by weight based on the total weight of fuel, oxidant and colorant. These additional salts may include metal salts of calcium, titanium, aluminum, magnesium, and the like. Metal flakes or particles may be added to the pyrotechnic compositions to provide a glitter effect. Suitable metals can include aluminum, magnesium, titanium and iron. Iron can generally be added in the form of steel shavings to avoid rusting problems from moisture.
One preferred pyrotechnic formulation includes a triazolyl-tetrazinyl-aminotriazine compound together with two parts ammonium perchlorate as the oxidizer for complete oxidation, with from about 10 percent by weight of a colorant. It is most preferred that the triazolyl-tetrazinyl-aminotriazine compound comprises a salt of cobalt or copper.
The pyrotechnic composition is formed from mixing or packing the triazolyl-tetrazinyl-aminotriazine compound, including its salt or complex, in an appropriate delivery combination for use as fireworks, with the appropriate mixing and packing being within the level of skill of a person of ordinary skill in the art of fireworks. The triazolyl-tetrazinyl-aminotriazine compound is diazotized from the triazolyl-triaminotriazine precursor, as taught herein, to form the appropriate pyrotechnic salt. Diazotization occurs by reacting the triazolyl-triaminotriazine precursor with a diazotization agent, for example nitrite salts, organic nitrites, and the like, such as, without limitation, nitric oxide, sodium nitrite, potassium nitrite and the like, with diazotizing agent known to those skilled in the art. The triazolyl-triaminotriazine precursor(s), including the acid salts thereof, are diazotized in an appropriate aqueous acid, such as for example hydrochloric or sulfuric acid, with the nitrite salt to give the ring-closed tetrazine product of the triazolyl-tetrazinyl-aminotriazine compound. The use of sodium nitrite (Zxe2x95x90Na) to form the triazolyl-tetrazinyl-aminotriazine compound is preferred. This reaction is represented below and in Examples 2 and 3. The triazolyl-tetrazinyl-aminotriazine compound (Zxe2x95x90Na) can be acidified to produce the parent acid of the triazolyl-tetrazinyl-aminotriazine compound (i.e., Zxe2x95x90H). Other triazolyl-tetrazinyl-aminotriazine compounds may be formed by neutralization of the parent acid or by cation exchange reactions with the sodium salt. 
The preparation of triazolyl-tetrazinyl-aminotriazine salts by neutralization of the parent acid (Method A) occurs by reaction with amine bases or by reaction with metal hydroxides.
Cation exchange with the sodium salt to form the triazolyl-tetrazinyl-aminotriazine salts (Method B) occurs by the process that includes an aqueous solution of the sodium salt being mixed with a solution of barium nitrate, strontium nitrate, calcium nitrate, or other.
The present invention further includes a chromogen for providing a colorant of a dye or pigment comprising a formula of: 
wherein R2 and R3 independently comprise electron donating groups, and Rx comprises an elongated conjugation sufficient to create a chromogen, with Rx preferably a chromophore, including azo dyes, having a (xe2x80x94Nxe2x95x90Nxe2x80x94) linkage or an imino dyes having a (xe2x80x94Nxe2x95x90CRaRbxe2x80x94) linkage, such as (xe2x80x94Nxe2x95x90CRaArxxe2x80x94), where Ra and Rb represent additional dye forming substituents, such as aryl groups, e.g., multiple and/or fused aryl groups (Arx). Representative units within the Rx group include anthraquinones, triphenylmethanes, azines, phthalocyanines, indoles, and the like.
In addition to the oxidative coupling reaction exemplified in Example 23 (Methods C and D), dyes may theoretically be formed by diazotization of the amino group on the triazole ring of an aminotriazolotriazine to produce a diazonium salt and then coupling the diazonium salt with various aromatic compounds. Preferably, an appropriate blocking group will be used on the triazine ring to prevent cyclization to form a tetrazine ring as occurs when the diazotization is performed on the [4,3-a]-triaminotriazolotriazine precursor. An example of a blocking group would be the methoxy group.
Preferably the dye comprises the formula: 
wherein R9, R6, R7, and R8 are electron donating groups, more preferably with R6 and R7 being xe2x80x94NH2, and most preferably with R9, R6, R7, and R8 are xe2x80x94NH2; and Ry is xe2x80x94Nxe2x95x90Nxe2x80x94.
Precursor
The precursor comprises a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt or its neutralized form of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The general process involves ring closure of 2,4-diamino-6-hydrazino-s-triazine with an acid and a chemical of the general formula RCN where the R comprises a leaving group, and then neutralizing the acid. 
More specifically, the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt is derived first by obtaining or synthesizing 2,4-diamino-6-hydrazino-s-triazine. One method for synthesizing this chemical is set forth in U.S. Pat. No. 3,061,605 by D""Alelio. The general method is to effect a reaction between 2,4-diamino-6-chloro-1,3,5-triazine and hydrazine. A specific example is set forth in column 3, lines 60-70 of the above patent which is hereby incorporated by reference. While this particular method of synthesizing 2,4-diamino-6-hydrazino-s-triazine is specifically disclosed, any prior art method of synthesis would be appropriate to practice the present invention. The 2,4-diamino-6-hydrazino-s-triazine is dissolved with an acid, preferably out at room temperature with an acid that is of sufficient strength to dissolve the 2,4-diamino-6-hydrazino-s-triazine. Many acids can be employed in the present invention, such as sulfuric acid or hydrochloric acid or mixtures of these acids with other solvents such as methanol or ethanol, and may be selected by one skilled in the art. One preferred acid is 1N hydrochloric acid. The dissolved 2,4-diamino-6-hydrazino-s-triazine is mixed with a reagent of the formula RCN, wherein R comprises a leaving group. This reaction will provide the amino triazole ring on the product directly. A leaving group, as used in this application, is a group that can be displaced to give ring closure; that is, produces the amino triazole ring. One preferred leaving group comprises bromine wherein the reagent comprises cyanogen bromide. Although the reaction in this step is acid catalyzed, preferred reaction times range from about twenty hours to about thirty hours in order to allow for the maximum formation of acid salt crystals. It is also preferred that the acid salt crystals be removed after the reaction is substantially complete, approximately thirty hours, to prohibit contamination of the final product with impurities. The crystals may be removed by any normal method, such as filtration, and can then be washed and dried in order to obtain the final acid salt product.
Neutralization of the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt crystals synthesized above to obtain a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine is accomplished by mixing the crystals with a substance more basic than 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This step results in the removal of the acid from the above reaction and provides for a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The substance used in this final step may be selected by one skilled in the art based upon the basicity of the substance versus the basicity of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. Some examples are potassium carbonate, potassium acetate, sodium bicarbonate, and sodium hydroxide. One preferred substance is potassium carbonate. It is also preferred that the reaction take place in solution, so preferably, water or some other solvent may be added to the salt.
The following examples (Examples 1A-1C) are preparations of the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine precursors, with the chemical structures shown below: